Shampoo



Patented July 2, 1942 Harrison Gunning, Brooklyn, N. Y.

No Drawing. Application October 9, 1987;

Serial No. 168,

3 Claims.

The invention relates to shampoo mixtures and more particularly to a novel and useful shampoo of the so-called dry type, wherein a copious foam or froth is formed on the hair and carries away the dirt, preferably without the addition of water then or subsequently.

Objects and advantages of the invention will be set forth in part hereinafter and in part will be obvious herefrom, or may be learned by prac-. tice with the invention, the same being realized and attained by means of the instrumentalities and combinations pointed out in the appended claims.

The invention consists in the novel compositions of materials, combinations and improvements herein shown and described.

The present invention is in part a continuation of my prior filed application Ser. No. 712,311, filed Februar 21, 1934.

The invention is directed to providing a novel and useful mixture to be used as a shampoo. An important object of the invention is to provide a shampoo which without the addition of water, forms a cleansing and dirt-loosening foam or froth, which may be removed from the head by simple wiping without causing subsequent irritation or leaving any undesirable residue on the scalp, and which has a distinct germicidal value in the treatment of dandruff and similar scalp afilictions. The shampoo of my invention may be designated as a dry shampoo to distinguish it from shampoos which require a subsequent water rinse to wash ofi the soap and other residue from the shampoo application, whereas with my invention the shampoo is soapless and the addition of water to initiate the shampoo and a subsequent water rinse are neither required nor desirable.

A further object of the invention is to provide a dry shampoo wherein the dirt, oil and foreign matter on the hair and scalp are attracted and carried away, largely mechanically, by the flotation action of the foam or froth. Accordingly,

the shampoo is designed to form a copious, strong and persistent froth which is capable of providing a very eflective flotation action. The ingredients .of the shampoo are combined so as to provide a soap or other lathering agent and as indicated, the character and action of the foam is radically distinct from those produced by such lathering agents. Moreover, as already indicated, the foam or froth created by my shampoo mixture may be squeezed off by the hands, carrying the dirt with it, while any residuum of the mixture left on the hair or scalp is germicidal and noninjurious thereto. The action of the froth or foam hereinbefore described is highly superior to that of a lather such as is formed by soap or other lathering agents. The foam formed in my shampoo has a very penetrating and searching cleansing action, the tiny bubbles forcing themselves into the mouth of the hair follicle and lifting out the dirt. The bubbles of this foam are strong, free and fairly dry and do not tend to cling to the hair or scalp as do the bubbles of a soap lather. The scalp is left in a very clean and free condition after treatment .with the shampoo.

In addition to the objects and advantages hereinbefore described, the shampoo of my invention contains ingredients which leave the scalp with a feeling of coolness and freshness. The cleansing and germicidal action of the shampoo is such that it is especially beneficial in overcoming scalp itching and irritation, yet this action is sufiiciently bland that there is no counter-irritating effect even from repeated use of the shampoo. Moreover, the head,'after shampooing, requires only a drying with a towel and it is possible for the recipient to go out immediately after washing the hair without danger of catching cold.

Broadly considered, the shampoo mixture or solution which I have discovered to embody the advantages hereinbefore referred to, comprises a mixed solvent, preferably an aqueous-alcohol mixture, containing'in solution one or more frothing agents and in addition, a salt or salt mixture designed to act as a mineralizer and pH regulator on the froth. In general the various constituents of the shampoo may be classified as follows:

shampoo of the present invention contains no (1) A mixed solvent (preferably water, and alcohol or its equivalent) having special advantages as hereinafter set forth, (2) frothing agents (such as essential oils, thymol, menthol, carva crol, etc.) a mixture of which has special advantages indicated below, (3) and buffer-salts to act as pH controllers and bubble mineralizers.

.Preferably also one or more of the ingredients should possess germicidal qualities and act as an agreeable odorant.

Referring first to the combined functions of the frothing agents and the alcohol-water mixed solvent:

It is known that water alone will dissolve small amounts of suitable frothing agents such as menthol, for example. If the surface of the water-menthol solution is suddenly increased as by agitating or rubbing the solution through the hair, a certain amount of foaming. or frothing will result. However, the available frothing agents, in general, have too low a solubility in pure water to be serviceable at their maximum efiiciencies. I have found that by using an alcohol-water mixture as a solvent, the concentration of the frothing agent or agents can-be increased to an amount such that a copious foam or froth can be easily produced.

In general, the primary function of the frothing agents, such as the essential oil or oils, hereinbefore mentioned, is to effect a flotation action on the entrained dirt, dead skin, scales, oil, etc., found on the hair. The action of frothing agents in flotation work is well known and need not be discussed in this disclosure. An explanation of the action of such agents in general flotation processes is to be found in standard works on that subject and reference may be had to Gaudins "Flotation (McGraw-Hill (30., N. Y., 1932, pages In the present invention, however, the normal activity and efiicacy of the flotant-frothing agent is very greatly enhanced by the use of a mixed solvent as hereinbefore described. That is, the flotation action on the materials to be removed from the hair is vastly intensified and rendered more effective by increasing (within certain limits) the concentration of the frothing agent in the liquid and this increased concentration is made possible by the use of a mixed solvent (e. g. alcohol and water) as explained above.

In general, I have found that the frothing agent should be an alcohol or phenol having at least six carbon atoms and at least one substituted group, linked to another carbon atom than the one to which the OH group is linked. In addition, certain oils containing such a compound or a non-ketonic derivative will also function as true frothing agents.

When a single frothing agent is used, the foam tends to be weaker and less permanent than with a mixture of frothing agents. It was found, for example, that although menthol and oil of Corylopsis were fairly good frothing agents when used independently, their total effect when used together was greater than the sum total of the two used independently. Indeed, when oil of,

elanthus by itself was investigated, it was found that the individual effects of the various constituents of this'mixedoil were very low in comparison with their total effect when used together, and the same is true with oil of Corylopsis, for example.

' When a number of frothing agents is introduced into the mixture, the relative concentrations of any one of the frothing agents in the surface and in the bulk of the mixed solvent will be widely different. Consequently, each frothing agent tends to produce 'a copious foam along with the others, but without any mutual interfering action one on the other; and therefore, the effectiveness of a mixture of frothing agents is greater than the algebraic sum of their individual eifectivities.

ing agents) and also explains why any cheaper frothing agent of individually greater effectiveness, such as carvacrol, may be substituted for Corylopsis with the same desirable result. It also explains why such small concentrations of menthol, thymol, and carvacrol are so effective when used simultaneously.

Other solvents than water-alcohol may be employed if it is miscible with water, a poor solvent for the basic buffer salt, has a low surface tension and a low viscosity. In general, the alcohol should be from 40% to 60% of the total mixture although as little as 25% may be used with fair results.

Practically, however, it has been found that ethyl-alcohol and water mixtures are by far the most satisfactory. In general, no alcohol or other solvent injurious to the human body can be used. This eliminates methyl-alcohol for use in a shampoo. Neither can alcohol of limited solubility in water be used. This eliminates all alcohols higher than the propyl alcohols.

A satisfactory basic buffer-salt is sodium bicarbonate. Potassium bicarbonate could be used, but it has been found that the potassium ionhas a harmful effect and that the foam is too dry, probably because of lower solubility of potassium bicarbonate in alcohol. The carbonates are unsatisfactory because they are too alkaline for the good of the hair. An alkaline sodium phosphate buffer mixture of pH 7.3 approx. is apparently satisfactory when used in sufiicient concentration. Sodium citrate itself may be used, but it is found that the foam thus formed is lighter than, and not so enduring as, that yielded by a sodium bicarbonate shampoo. On the other hand it is found that if a small amount of citric acid is used together with sodium bicarbonate the resulting solution is even less alkaline and at least equally effective.

Such alkaline salts as borax and sodium cinnemate give a wetter, less permanent foam, probably because of 'some slight solubility in the alcohol. Soaps, which are soluble in alcohol, act entirely as one might expect soaps to act. The lather is soapy or slimy and not dry, not at all like a desirable slightly alkaline buffer-salt foam.

Desirable proportions of the various constituents of the shampoo are as follows: i

The mineralizer salt should be present in concentration just below its saturation value in the bulk of the liquid at normal temperatures.

The alcohol should be present in such'concentration as to provide a wide differential in the solubilities of mineralizer in the bulk and in the surface of the liquid. The concentration of alcohol must not be so high as to unduly increase the solubility of the frothing agent nor so low as to require an excessively high concentration of buffer-salt in order to get the mineralizer effect.

As already pointed out, a plurality of frothing agents each present in small concentration is 'superior to one frothing agent in large cencentration.

In addition to the frothing agents, I have found it desirable to employ froth increasers or foam driers which tend to increase the stiflness of the foam and render it stronger and apparently capa- The foregoing explains. the eflectiveness as a frothing agent .of a mixed essential oil, such as ble of supporting more dirt and foreign matter. These foam driers are alcohols, phenols or ethers having only one oxygen containing radicle of any particular kind, having at least six carbon atoms in the molecule, but not including a ketone group, or they may be esters of true frothing agents.

or an ester having at least four carbon atoms in the alcoholic radicle and at least six carbon atoms in the acidic radicle.

The following formulae give embodiments of the invention for practical commercial application, but it will be clear that the invention is not limited to specific quantities, proportions or materials beyond the extent indicated in the foregoing discussion:

Grams Grams Water 57. Water 57. 00 Sodium bicarbonate 1.20 Sodium citrate 3.00 thol 0. l 0. 15 0.03 0.03 Carvacrol 08 Carvacrol 08 Ethyl alcohol 95% l 41. 00 Ethyl alcohol 95% 41. 00

(C) In Formula A the pH may be decreased by adding small quantities, for example 0.10 gram of citric acid.

Another formula which has proved very satisfactory is as follows:

In this formula, the menthol, borneol, tertiaryamylphenol, carvacrol and geraniol 'act as true frothers, while the terpeneless oil cf "nay acts as a foam drier.

Many other substances, within the class defined, will operate a frothing agent and in place of menthol, there may be used:

- Grams Isoborneol 0.22

Santalol 0.12 Chavicol 0.12

Thymol 0.16 Terpineol 0.16 Rhodinol 0.16

Linalool l 0.16

Cintronellol 0.16

the amounts given being the approximate optimum concentration for each substance when usedalone. When mixed with other frothing agents, the amounts will generally be reduced, and the combined effect will be greater, as a rule, than the effect of any one. In this way, not only may the desired odor be produced, but the foam may be increased.

In addition to the foregoing frothing agents, there may be used small amounts of one or more of the oils of sandalwood, vetiver, patchouli, camphor sassafrassy, or thyme, or of compounds such as hexylrescorcinol, ditertiarybutylpyrogallol, phenylbenzylcarbinol, phenyltolylcarbinol, tertiarybutylphenol, butylphenyl-carbinol, cetyl alcohol, orthocresol. Certain of these pure compounds are not indefinitely stable and for that reason their use-is not commercially feasible.

Of the frothing agents listed, menthol, borneol, lsoborneol, thymol, carvacrol, terpineol,

geraniol and the oils of sandalwood, vetlver, r

patchouli, camphor sassafrassy and thyme-are suficiently good frothers to be used alone to produce an abundant foam, which may be increased by using one or more of the other frothing agents and foam increasers. However, substances such as thymol, carvacrol and orthocresol must be used with caution because of their irritant effect upon the scalp.

As foam driers, or froth increasers, up to 3 drops of one or more of the following substances may be employed: phenylmethylcarbinol, cinnamic alcohol, benzylalcohol, triphenylcarbinol, cholesterol, normal butyl-, iso-butyl-, normal propyl-, isopropyl-, isoamylor secondary hexylalcohol, saifrole, anethole, eugenol, isoeugenol, cineole, methyl eugenol, heliotropin, diethylphthalate, dibutylphthalate, isobornylacetate, benzylacetate, benzylbenzoate, phenyl-aceticaldehyde, oil of pimento, oil of eucalyptus and terpeneless oil of bay.

The aliphatic alcohols listed immediately above are not generally desirable astheir effect is rather slight and better effects may be obtained from others of the compounds. -The drier effect may also be obtained by larger quantities of triethylcarbinol, methylisopropylcarbinol, methylbutanol, cyclohexanol, tertiary amyl alcohol, secondary amyl alcohol, secondary butyl alcohol, tertiary butyl alcohol and dimethylethylcarbinol. However, the effect of these aliphatic alcohols is not generally apparent until after several days.

The method of using the shampoo is as follows:

About one and one-half ounces are rubbed into the hair and scalp bypouring small quantities into the hollow of the hand and rubbing rapidly.

and briskly into the hair. The froth or foam forms almost immediately with rubbing. When the entire head is well covered, the froth is squeezed off rapidly with the hands, and the head driedv immediately with a towel. This should be accomplished in less than three minutes. The froth should be removed before it has begun to decrease appreciably from its maximum formation. The washing is preferably repeated by a second application of the product. If dandruff, scaly scalp or other-unhealthy condition is present, a second shampoo three days after the first should be made. This will usually b sufficient' to eliminate dandruff and to thoroughly clean the hair and scalp, and to remove all dirt and thoroughly sterilize the scalp. The wholewashing requires only about five minutes, the hair being combed immediately.

The foregoing directions apply to the use of the shampoo by men. For the average woman's head, it is preferable to use a single application totaling six or seven ounces, the excess foam being floated off as additional shampoo liquid is applied.

It will be understood that the foregoing statements of theory are based upon my present understanding, of the invention through extended research and use thereof, but the invention is not limited to any particular theory explaining its operation.

The invention in its broader aspects is not limited to the specific compositions shown and described but departures may be made therefrom within the scope of the accompanying claims without departing from the principles of the invention and without sacrificing its chief advantages.

What! claim is: gredients in substantially the proportions indi- 1. A foaming soaLpless shampoo comprising subcated: stantially the following proportion of ingredients: Grams Grams Water 57.00 5 Sodium bicar 1.20 water Menthol 0.15 Citric a Carvacrol 08 Boric arid 0.10 Sodium bicarbonate 1.20 Ethyl l h l 95 m 41. Ethyl alcohol 43.00 10 A Shampoo wmpl'ismg the followin! Mentho1 on gradients in substantially the proportim indi- Borneol 0.04 cited! Carvacrol 0.07 Grams Tertiaryamylphenol 0.07 water 57-00 Geramol f 0 03 Sodium bicarbonate; 1.20 011 of ba. ter neless 0.03 Menthol y EthyI alcohol 41.00 2. A shampoo comprising the following. in- HARRISON GUNNING. 

